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Patented sept. 27, 1938 y ormwmm'rommma or to I. G. Farbenindusti-leAktien'gc cllsc gg;

FrankIort on-the-Main 'tion or a 'm' aanaflmmam,macarlal ,No.

, am. In

for'v'a'rying their amnity. v

One of its objects is a process'jot treating-ma V terials for varyingtheir aflinlt'y. Another ob- 5 ject is the material obtainedby'this-proce'ssr Fur- 'ther objects will be's'en iromthe detailedspeciflcation iollowinghereinafter.-

According to the present mvehunnjlt has been found that. the chemicalbehaviors: naturalor l0 artificial products from proteins orof materialscontaining or consistin g oi highly molecular materials which are'notproteins but'c'ontain vbasic nitrogen towards dyestuffs can beconsiderably changed if'they are treatedwith an allgvlating agentselected from the group consisting of esters and diazoparafllnsgiorinstancefwith' a reactive alkylester of'a minerafacid or a mixedorganicinorganic acid as for instance alkylor aryl-sulionic acid. Inthiscase apparently alkylated a products'are formed the electrochemicalcharacter of which is different from that of the starting materials. Theallwlation takes place at-thenitrogen atom,- however, a change-of theelectro ."che'mical character is also eflected byalblation oLcarboxylgroups. as for instance in the case or w'ool. Alkylating agents of thiskind are 101' iristance, ethyliodide, ethylbromide, n-butyliodide,ethylenechlorhydrine, -benzylch1oride, p-nitrobenzylchlo'ride,chloracetic methylester, .chlor- '30 acetone, chloracetaldehyde,dialkyisuliate, alkyl- 'suli'onic acid alkylesters, the sodium saltoichlormethylbenzene sulionic acid, the sodium 'salt 01 a xylol sulfonicacid halogenatedin the side. chain, toluene sulfonic'acid alkylesters,naphthalene sulfonic acid alkyl estersysalts or carboxyaryl sulionicacidalkyl esters; ttrichloroxypropylamine hydrochloride,p-tris-pechlorethyl-aminehydrochloride and tetrachloroxypropyl ammoniumchloride, diazo paramns such diazoethane.

, The extent to which the material is-ichanged is mainly dependent uponthree factors. namely, the swelling condition of the material. the-reae= tivity of the agent .and the temperature. The conditionsof'reaction under which for instance,

a sufllcient coloring eifect is obtained may therefore vary widely.Apart irom the fact that from case to .case, the demands vary, forinstance, ac- 1 cording to whether a relatively slight improve- 'ment ofthe dyeing. capacityis desired particularly when working. in a neutralbath orwhether a-strong coloring'contrastis desired In the, case ofgwooland other animal fibers preferablya temperature oi at least 40f; C. isapplied when'work- 65 ing in non-aqueous solutions, sincewith this tem-1, This invention relates to, a 'treatme'nt oima-' peraturethe-reactivity"ofthe 'materia increase. a .e M I I 11' forspecialreasonsfitis desiredto \lvorlr"at v asdiazo'methanei'or' I I t tA mayber'eversed ,1, t, a

v ng the suble'ct matter oi: f the invention may be applied at ordinaryor'raised' .temperature, the limits .dependingjbnthe reac-= ativi'ty ofthe alkylating agent and the resistance ofthe goods-under treatment,The'speedof the reaction may also be influencedby the moisture in theatmosphere or in the} goods under treatawe-- p December; 8

tem r u lowerthaj w prolong the; periodfoi reaction.

yantageously' easily'freacting, alkylating' agents i are "used, forinstance, air-alkyl mama, "any case; aboiling oifdry wool witnemymrpm demr two hours gives {no effect. lilsolwhenf imparting a strongerreactivity to wool by expaangi it to the influence or an atmospherecontaining ;per cent of relative moist'uri'e the influence 1 is onlyvery slight 'andpractically without val'ue as experlments have shown;vA-reaction period of at least 3 hours is necessary""i'or the productionof; a ma1- terial' which has clear-ly a ,greaterjg amnity to acid 1dyestufl. than; the -nontreated fmateriaL gAlso F" when treating wool;withf dimethylsulfate in" an alkaline imediu'ml at: room-temperature no.

eflect is obtained iiithe'galkylating agent; is';not

finely dispersed or emulsified in the aqueous ;me.- 'However, an effectismmducedaii;wooljis boiled in -.'methanol in the; presence of, :10 R or=;20 7 percent or. dimethylsulfate wher by; heca ition of an' acidbindingsagentfiacilitatesthe re,- action; In-"the same manner a -strongeiiect 318 produced it woolis treated with;an;aryl,su1ionic 1;;

presence ot an acid pared chalk. v

acid allryl ester in an;aqueous, suspension.in the" treated is more ;or;less profoundly changed; in 1 i particular theadsorptivecapacity and thespeed oi fixation oi! the dyestuffs, dyestumderivatives, dyestuficomponentsv and other-treating agents having acid groups, are g'enerally'considerabLv enhanced, whil inthe; case or basicdyestuiis the I reverseeflectoccurs. ,Wherijthe alkylating agent contains acid groups .Itheforegoing relationships The treatment to merit. In the gcasi'of halogencompounds, which react slowly, the chemical change ambassajte'ned by a,smalljaddition of an' iodidejforexa'fnpie, potassium iodide,tetr'amethyl ammonium i o'-' dide ,or,trimethyldodecylarnifionium"iodidealready mentioned, theprocessrnay also v ductedin the presencefofr aneutral or alka acid bindingf-ag'ent; for *example in the 'e ofpotassium acetate, borax, sodium phosphate, sodium silicate or of amineswhich are alkylated with difliculty. V obtainedwhen the treatmentisconducted with reactive esters of organic acids in the presence ofalkylene'oxides or their analogues, for example propyleneoxide orepichlorhydrin. There may also be present in the processadditions'oi'jother' reactive materials named in U. S. patent applicatlon-Ser.No. 40,352 filed September, ,12, 1935 v rurthermora'agents capablefi'oiprotecting the fiber, oxidizing or reducing bleaching agents and Iswelling agents such as iorma'mide, thiourea,

magnesium thiocyanate, zinc thiocyanate and methanol may be present."The .alirylati'ng' agents may be used in the process assuch or beproduced or liberated in the presence of the goods to be treated, forexample by thermal decomposition of labile alkyl halides orsalts, ofimine-ethers, or nitrosoalkylurethan'es. "1 v The action oi thealkylating agent can be com- .bined witha drying or printing operation;,Also

an alter-treatment, oi. afinished dyeing may. be advantase ai r h urp ep m rov ns h iastness thereon. In both cases'it is obvious that thedyestui! mustnot be essentially changed by the alkylating agent. Thefiber may be P 31- treated; before the alkylatingoperation withmaterials other than, dyestutls for example with mordants,tanning-agents, loading agents or in"- secticides. The after-treatmentoi'finished colorings with alkylating agents is ".01particularimportance because in, thismanner an increased da'stness isobtaineds. In both cases it must be considered thattheshadeotsome dyesis changed. By changing the pH value ot the substrate a changing oithe'shade oizthe coloring maybe pre essential extent, adsorbs Alizarinevented or lessened. *.'.-The changingoi the coloring increases generallywithan increasing, pH value.

Substances which 1 are sufliciently volatile at low or moderatetemperature and, if desired, under diminished pressure, areadvantageously applied to thegoods in the tom 0! vapor in the mannerdescribed in'my co-p'ending application Ser. No.

48,445 filedOctOb er 23, 1935: I

The increase ofthe afllnity or-the :speed adsorption exhibited by thefibers or 'objects for certain groups oi dyestufls whichi'ollo'ws theapplication ofthe invention is of particular importance in'printing andin'dy'eing mixed fabrics or mixed yarns, for instance mixedyarns of wooland cellulose fibers orot wool and acetyl-cellulose fibers, particularlywhenjthe dyeing is tc J be conductedunder ieebly acid or'neutralconditions at the lowest'possible temperature.

, The following; examples illustrate the invention, the parts being byweight unless stated otherwise, and the parts by weight and parts byvolume bearing the relationshipjto each other asth'at oi the kilo to theliter: 3

having a moisture saturation of '15 per cent.{ The wool, whichis'externally altered only to an unorOrange 11 (each 2 per cent.), in aneutralliquor much more strongly than woolwhich hasnot been treated. andis .dyedin the same dye-bath.

dyeings are also faster to washing than equally deep dyeings onuntreatedwool. The samedyeing diflerences are observed ii. the wool issoaped beforedyeing. Orange 11 (Schultz, 7th edition, Vol. 1, page 86).

A particularly strong .eirect-is I sample.

I proved. 80 C. ror 14 hours in '1000 parts by volume oiiain containing0.5 part oi vapor oi. eth l bromide and ect Blue A Alizarine Direct BlueA (Schultz, Vol. II, page 9, 7th edition).

named Idyestufis'are adsorbed by the material at an essentially lowertemperature than by normal lrample 3.'Wool is impregnated with asolution of sodium benzyl-chloride-sulphonate oi! 10 per cent.strengthcontaining mol. of potassium iodide, calculated on thebenzybchldride-sulphoate. The *wool is then centrifuged and heated for16 hours at 7010. Acid dyestufls, for instance Alizarine' Direct Blue A,are more quickly fixed by the treated material than by ordinary wool.

Example 4.Wool is heated ion 18 hours. at 80] C. in an atmosphere of 75per cent. moisture saturation and, containing "be'nzyl (chloride.amounting to 20 percent. or the weight of the wool. The treated slreinis still puife'white. When dyed with sum-me DirectBlue A the dye isstrongly adsorbedby' the treated material alreadyatBO'C. Even afteranintermediate treat-j ment with ammonia, the samerelative difference uts- Example 2.' Instead oi the ethyl bromide prescribed in the foregoingexample, chloracetic acid-ethyl-ester is similarly used, the duration ofthe operation being 16 hours at C. and under a moisture saturation ofper cent. The above-' "Ex mple 5.,-wooldyed films be as; a!

Orange, IIis treatedji'or ld hours at 50 C. in an atmosphere of '15 percent. moisture saturation with ethyliodi'de vapor. 'Iheliastn'ess towashing is 'considerably improved. In like. manner the i'astness tolwashing of a cent. dyeingoi Azofuchsin'e 'Gpn'wool m'aybeenh'ancedr.Ea:ample "6.Woo'l is (impregnated with-an n/ 5 -solution oitetrachlorhydroxypropylammonium chloride obtainable according toU. S.pat- .ent application Ser. No. ssoosme December 5, 1935. (of. BritishPatent .No. 454,320); and after having been centrifuged is heated for ldhours at Direct Blue A than an untreated comparative Ezamplei-Fibroinisms i heated for 16 hours at C. in an atmosphere of moisturesaturationoi, 75 per cent. in the presence '0'! ethyl- The .treatedartificial-silk is dyed with Orange n not inconsiderably darker tintsthanuntreated artificial silk in the same bath.

iodide vapor.

Example 8.-'-.-An acetateiartiflcial sillrcontain- 80 C. After thoroughwashing, thetreated wool is more powerfully dyed bymeansot -Alizarineing a basic artificial resin 01! thepolyvinyl series (content of basictertiary nitrogen-in the fiber being 0.4 per cent.) isdyed, with 2 percent. of Alizarine Direct Blue A in the presence 01' acetic acid. Thedyed material-is suspended for 14 hours in an atmosphere of 80 per cent.moisture saturation containing ethyliodide vapor. The iastnes's towashing'oi the dyeing is not inconsiderably im- Emmple =9.-'--Zephir5.... is dyed in the usual manner with 3 per cent. of Amidonaphthol-Red'7 BB -(Schuita1Farbstofltabellen' 'Ithed. suppl. vol., page 8, No. andis then'heated for 12 hours with -8 per cent or-propylene oxide and20per cento't'ethyliodide in" an atmosphere containing about 92 "per centof relative moi'sture in a closed vessel of '100 parts of volume at 50C. The aftertreated wool can be washed at'80 C. withoutmaterial changein the'color and without bleeding on white material washedsimultaneously. The

non-atter-treated coloring is removed to the greater part when washedunder the same conditions.

colored. v Ezrample.10.10 parts of zephir yarn are treated with anaqueous dispersion of 5 parts of. prepared chalk and 5 parts oftoluenesulfonic acid methylester both being dispersed with per cent ofoleylpolyglycol, for 1 hour at 65? C. and for 1 hour at 75 C. in a bathcontaining 20 parts of liquid on one part of yarn. Then the yarn isthoroughly washed and treated with a soap solution. The treated wool-isdyed more intensely with an acid dye, for instance, with Alizarine;Direct Blue A (Schultz Farbstofitab. 7th ed. ,vo1;--

II, page 9) than the starting material.

Example IL- Zephir-Wool is treated with 15' per cent of ethyl bromideand 10 per cent of'1.2-

, propylene sulfide-for 14 hours at50 C, in an material to be treated.The thoroughly washed; material is, in a neutral bath, dyed by nieansofatmosphere with 75 per cent of relative moisture.

The wool shows an appreciable improvement of the capacity of being dyed,particularly in a neutral bath. a The colorings ,for instance, withAmidonaphthol-Red BB (Schultz Farbstofltab, 7th ed. suppl. vol., page 8,No. 110) are faster to water and washing than those of the untreatedwool.

7 Example 12.--Wool is treated withan aqueous dispersion of 20 per centof dimethylsulfate and- 20 per cent of prepared chalk made with the aidof oleyl-polyglycol, for 2 hours at C. ina' bath.

containing 20 parts of treating liquid on 1 part of acid dyes, forinstance, of Orange I1 much more fibers containing a basic artificialresin, and artiintensely than untreated material dyed in the same bath.Rinsing with a cold solution of ammonia before dyeing will not make thepretreatment inefiective. If a material -.is dyed which contains treatedand untreated material, strong two-color eiTects are obtained. What Iclaim is: v

1. A process of increasing the aifinity fcr acid' dyestuffs of wool,natural silk, leather, artificial fibers containing a basic artificialresin, and artificial fibers containing a basic cellulose derivative,

which comprises subjecting the material" to the" action of an alkylatingagent selected from the group consisting of reactive alkyl esters anddiazo- 2. A process of increasing the afllnity foracid dyestuffs ofnatural and artificial organic products containing a quaternary aminogroup, to-

ing of reactive alkyl esters and diazoparafiines.

'3'. A process of increasing the affinity for acid dyestuffs of wool,natural silk, leathenartificial ficial fibers containing a basiccellulose derivative, which comprises subjecting the material to theaction of a reactive alkyl ester. J i e 4. A process of increasing theafllnity for acid dyestuffs of wool, natural silk, leather, artificialfibers containing a basic artificial resin, and artificial fiberscontaining abasic cellulose derivative, 1 which comprises subjecting thematerial to the action of a diazoparamne.

f-x 6;;A process-10f the alkyl radicals are methyl groups.

dyestuffs of wool,lnatural silk, leather," artificial fibers, containinga basic artificial resin, 'andar'ti flcial fibers containing a basiccellulose'derivative,

which comprises subjecting the material'to the alkyle'nesulfides.andalkyleneimines.

group consisting of reactive alkyl-esters'anddiazo 5. :A' was is:increasing the aflinity' tor and increasing the ailinity ior acid idyestufls of wool, natural silk, leather, artificial fibers containingabasic artificial-resin, and arti- 1 j I '1 .flclal flbers'c'ontainingarbasic' cellulose derivative,

which; comprises subjecting the material'to' the 1 parafllnes in ,thepresence of a swelling agent;

17.; A process of "increasing the afilnity to acid 2 I fiberscontainings; basic artificial resin, and arm .n

dyestufis ofQwool, natural silk, leather, artificial ficialfibers'containing a basic cellulose derivative,

which comprises subjecting the: material to the L actionoi analkylatingagent selectedirom' the; 1 ,groupconsisting of-reactive alkylesters and diazoparafiines, andlsubsequentlydyeing the material 8; Aprocess of increasing the afilnity to acid dyestuffsof.woo1',.natura1silk;leather,artificial fibers containing abasicartificial resin, .and-arti-" 'ficial fiberscontaininga basiccellulose derivative, which comprises subjecting the material to the 1action of an alkylating, agent selected from the a group consisting ofreactive alkyl esters and diazoparafilnes, and simultaneously dyeingthe' material 9. A process of increasing the 'aifnity to acid dyestufislof wool, natural silk-leather, artificial f4 a'fiberscontaining a basicartificial resin, and artificial fibers containing a basic icellulo'se,derivative,

whlch comprises dyeingthe material'with an acid;

dyestufi, and subjecting it] to the action of an alkylatingagentz'selectedfrom the group consist- Q I ing of reactive alkyl estersand dialzoparafiinesi 10; An article comprising one of the group of:

4s}, materials consisting of wool, natural silk, leather;

artificial fibers containing abasicartificial resin,

derivative, said materialsbeing substituted-(by:

alkyl radicals and having a substantially increased 56 j; I afilnlty foracid dyes] gether with a carboxyl group, combined in molecules ofihighmolecular weight, which comprises subjecting the material to the actionof an alkylating agent selected from the group consist- 1 fibershaving'incorpo te abqsiq artificial resin, I substitutedbyalkylradicals,

13. Acetyl cellulose fibers havinga substantially increased aflinity foracid dyestufis, saidacetyl cellulose fibers'having'incorporated a basicartif ficial resin substituted byalkyl radicals.

- 14. An article as defined in claim1 10, infwhic1r.;

and artificial fibers'containing a basic cellulose raunscmncn.

